This study has revealed the advantages of synchrotron radiation high-energy X-ray fluorescence spectrometry (SR-XRF) utilizing 75.5 keV X-rays at SPring-8 BL37XU for trace elemental analysis of forensic samples. The lower limits of detection (LLD) values calculated from calibration curves were pg levels for Ba, Ce, and Sm and 10 pg levels for Sr, Zr, Sn, and Hf. K-line peaks of 31 elements, including rare-earth elements, could be detected in the spectrum of NIST SRM 612 glass and the relative standard deviations (RSD) of all the measured elements except Ca were less than 9.7%. Fragments from collected 6 sheet glasses were used in order to examine the capability of this technique of forensic discrimination of glass fragments. Several trace elements such as Pb, Rb, Sr, Zr, Mo, Ba, La, Ce, and Hf were detected in these samples and could be used as important indexes to characterize the glass samples. This technique can provide an effective approach to the nondestructive discrimination of small glass fragments.